JP3015898B2 - Dispersion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a dispersion useful for an organic polymer or as another raw material.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as calcium carbonate, clay minerals, and mica have been mixed and kneaded in order to improve various characteristics of organic polymer materials such as polyester and polyamide, especially mechanical characteristics and heat resistance. Is being done. However, simply mixing and kneading these inorganic materials does not readily disperse the inorganic materials into fine particles and do not disperse them. Therefore, a material having satisfactory properties has not been obtained. For this reason, many patent applications have been filed for inventions aiming at uniform dispersion in an organic polymer, in which montmorillonite and a fluoromica-based swelling clay mineral are chemically treated to form fine particles, and are dispersed uniformly in an organic polymer. Examples thereof are JP-A-62-74957, JP-A-2-173160, and JP-A-3-77.
No. 29, JP-A-3-41149, JP-A-8-
3310, JP-A-8-59822, JP-A-8-120071, and JP-A-8-134205. However, at present, even with these methods, sufficiently satisfactory dispersibility has not been obtained.

[0003] Further, there is a report on "ordered structure of swellable mica in an aqueous phosphate solution" (Abstracts of the 40th Clay Science Symposium, 1996, pp. 90-91). No mention is made of dispersions. JP-A-6-2
JP-A-99104 discloses an aqueous paint clay modifier comprising a smectite clay mineral and a condensed phosphate, but has a different purpose from the dispersion of the present invention. Neither is it stated what properties are to be found.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a dispersion which is more useful as a raw material for an organic polymer which is expected to further improve the dispersibility obtained by a conventionally reported method and which is expected to have more functionality. Another object of the present invention is to provide a dispersion liquid useful as a property improving agent or a property imparting agent for various other materials.

[0005]

In order to uniformly disperse an inorganic material in an organic polymer, it is extremely important that the inorganic material be uniformly dispersed in a monomer which is a raw material of the organic polymer. Based on the knowledge gained from the conventional experience of the fact that the dispersion is repeated, various tests are carried out, and the dispersion prepared under certain conditions has unprecedented characteristics, so that it is expected that functionality is also unprecedented in terms of functionality Find out what you can do,
The present invention has been completed.

That is, the present invention includes the following inventions. (1) A dispersion obtained by mixing a swellable layered silicate, a potassium salt and a solvent. (2) The dispersion according to (1), wherein the potassium salt is potassium pyrophosphate and the solvent is water and / or glycols. (3) A dispersion for producing a polymer obtained by mixing a swellable layered silicate, a potassium salt and a solvent.

(4) The dispersion according to the above (3), wherein the potassium salt is potassium pyrophosphate and the solvent is water and / or glycols. (5) A polymer monomer dispersion obtained by further mixing a polymer monomer with the dispersion according to any one of (1) to (4).

[0008]

DETAILED DESCRIPTION OF THE INVENTION As described above, the present invention provides a dispersion obtained by mixing a swellable layered silicate, a potassium salt and a solvent, and a dispersion obtained by further mixing a polymer monomer with the dispersion. And a polymer monomer dispersion obtained. The details of the swellable phyllosilicate, potassium salt, solvent and high molecular monomer which are the raw materials of these dispersions are shown below.

The swellable layered silicate swellable means that water or an organic solvent penetrates between crystal layers in water or an organic solvent and swells, and forms an element constituting a main constituent layer and an interlayer material. The degree of swelling varies depending on the type of element, resulting in so-called free swelling or limited swelling, and any of them can be used in the present invention. These swellable layered silicates disperse in water as flaky microcrystals.

The crystal structure of the swellable layered silicate used in the present invention is such that the tetrahedral sheet (A) and the octahedral sheet (B)
A: a main constituent layer (2: 1 layer) combined in a ratio of B: 2: 1, and an interlayer material composed of cations between the layers to balance charges,
Its cation exchange capacity (methylene blue adsorption amount) is 15
Those having a range of 150 to 150 meq (milliequivalent) / 100 g are preferable, and 50 to 150 meq (milliequivalent) / 100 g.
Are more preferred. Further, the swellable phyllosilicate used in the present invention preferably has an average particle size of 0.1 to 50 μm, and when the particle size is large, it is preferable to grind it.

Specific examples of the swellable phyllosilicate used in the present invention include, for example, natural or synthetic hectorite,
Smectite group clay minerals such as saponite, stevensite, beidellite, montmorillonite, nontronite, bentonite and Na-type tetrasilicic mica,
Swelling mica group clay minerals and vermiculite, such as Li-type tetrasilicic mica, Na-type fluorine teniolite, and Li-type fluorine teniolite, or substituted or derivative thereof, or mixtures thereof. The above-mentioned substitutes include those in which a part of Na ⁺ or Li ⁺ ions of interlayer ions are replaced by K ⁺ ions, and those in which Si ⁴⁺ ions of tetrahedral sheets are partially replaced by Mg ²⁺ ions. Included.

Commercially available products include Laponite XLG (a synthetic hectorite-like substance manufactured by LaPorte, UK), Laponite RD (a synthetic hectorite-like substance manufactured by LaPorte, UK), and Thermabis (similar to a hectorite manufactured by Henkel, Germany) Substance), smecton SA-1 (a saponite-like substance manufactured by Kunimine Industry Co., Ltd.), wenger (natural montmorillonite sold by Toyshun Yoko Co., Ltd.), kunipia F (natural montmorillonite sold by Kunimine Industry Co., Ltd.), veegum (US , Natural hectorite manufactured by Vanderbilt Co., Ltd., dimonite (synthetic swellable mica manufactured by Topy Industries, Ltd.), somasif (ME-100, synthetic swellable mica manufactured by Cope Chemical Co., Ltd.), SWN (corp. Synthetic smectite manufactured by K.K.), SWF (synthetic smectite manufactured by Coop Chemical Co., Ltd.), etc. And the like.

[0013] Among the swellable layered silicates described above, selected from sodium and / or lithium obtained by heating a fine powder obtained by mixing talc with sodium and / or lithium silicofluoride to 700 to 1200 ° C. A swellable layered silicate containing alkali metal, magnesium, silicon, oxygen and fluorine as main constituent elements is preferred. The details of the swellable layered silicate produced by this method are described in JP-B-6-27002, and the above-mentioned Somasif (ME-100) is obtained by the production method.

Potassium salt Any potassium salt dissolved in water or an organic solvent used as a solvent in the present invention may be an inorganic potassium salt or an organic potassium salt, and is not particularly limited.
Specific examples include potassium pyrophosphate, potassium triphosphate, potassium polyphosphate, dipotassium monohydrogen phosphate, potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, potassium oxalate, potassium acetate, potassium citrate, and the like. Particularly preferred is potassium pyrophosphate.

Solvent As the solvent, water, an organic solvent or a mixed solvent thereof is used. Alcohols (lower alcohols such as methanol, ethanol, propanol, etc.) as organic solvents
And / or polyhydric alcohols containing glycols are preferred. Examples of glycols that can be used as a solvent include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, 1,4- Bis (β-hydroxyethoxy) benzene, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can be mentioned.

In the present invention, a raw material for producing a polymer compound such as a synthetic resin is referred to as a polymer monomer. In the present invention, the term “polymer monomer” is a concept including a low-polymerized polymer which is a raw material for producing a polymer compound, in addition to a monomer generally referred to. In the present invention, one or more kinds of polymer monomers are used. The monomers of polyamide and polyester, which are typical polymer compounds, are described below.

Specific examples of the polyamide monomer include 6
-Amino-n-caproic acid, amino acids such as 12-aminododecanoic acid, nylon salts such as acipic acid salt of hexamethylenediamine, ε-caprolactam, butyrolactam,
Lactams such as valerolactam, capryllactam, dodecanolactam and the like can be mentioned.

Specific examples of the polyester monomer include:
As dicarboxylic acids or diesters thereof, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid , 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diglycolic acid, dimethyl terephthalate and the like;
Ethylene glycol as a diol (glycol)
Propylene glycol, 1,4-butanediol, 1,
Examples thereof include 6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, 1,4-bis (β-hydroxyethoxy) benzene, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

The method for producing the dispersion of the present invention is described below, but is not limited thereto. Normally, the swellable layered silicate is dispersed in a solvent, but the swellable layered silicate may be dispersed in a solution in which a potassium salt is dissolved in a solvent. In particular, when the solvent is a glycol, the latter is preferred.

Water is usually used as the solvent, but an alcohol (lower alcohol such as methanol, ethanol, propanol, etc.) and / or a polyhydric alcohol may be mixed in some cases. If the dispersion is good, the dispersion may be carried out in alcohol (lower alcohols such as methanol, ethanol, propanol, etc.) and / or polyhydric alcohol without using water, and particularly in glycols which are also high molecular monomers. And a useful dispersion may be obtained.

The concentration of the swellable phyllosilicate is not particularly limited, but it is usually mixed so as to form a dispersion of 1 to 20% by weight. Stirring is sufficient to improve dispersion. Next, a potassium salt is added to the dispersion containing the swellable layered silicate. Usually, the amount of potassium contained in the potassium salt is 0.05 to 1 mol per 1 mol of the swellable layered silicate.
Add an amount to give 10 (mole or gram ion). Since the added potassium salt needs to be dissolved in the solvent, it is added if the solvent is insufficient. As described above, the potassium salt may be first dissolved in a solvent, and then the swellable layered silicate may be added to the solution. In addition,
In the series of operations so far, there is no particular problem as long as the liquid temperature is about 0 to 60 ° C. Thus, the dispersion of the present invention is obtained.

Next, the characteristics of the obtained dispersion will be described. In the dispersion obtained by dispersing the raw material swellable phyllosilicate in water, the bottom space value (d ₀₀₁ ) of the swellable phyllosilicate is determined by the X-ray diffraction pattern to obtain a card house structure (0).
01) No reflection peak value (6 to 15 °) near the diffraction line region was observed, and in a dispersion obtained by mixing sodium tripolyphosphate with the dispersion, a reflection peak near the (001) diffraction line region was clearly observed. You.

However, the X-ray diffraction pattern of the aqueous dispersion of the present invention (the dispersion of the present invention when the solvent is water) is (0000)
1) The reflection peak near the diffraction line region is not clearly recognized,
A very weak broad peak is observed around 15.4 to 15.5 °. This is because the interaction between the particles of the swellable phyllosilicate dispersed in an ultra-thin state is effected, and the swellable phyllosilicate is formed of tabular grains while sandwiching two water molecules. It is judged to indicate that they are slightly overlapped and laminated between the ends. This peak does not exist in the aqueous dispersion composed of only the raw material swellable phyllosilicate.

A comparison of the X-ray diffraction patterns of a dispersion obtained by dispersing only the raw material swellable phyllosilicate in water (hereinafter referred to as “elementary dispersion”) and the aqueous dispersion of the present invention shows that In the dispersion, the strength at a low angle (2θ = 1 to 3 °) is very weak as compared with the elementary dispersion. This means that in the case of the elementary dispersion, a short-range interaction between the dispersed particles of the swellable phyllosilicate acts to produce a reflection peak based on a disordered interparticle distance at a low angle. This indicates that in the aqueous dispersion of the present invention, the interaction at a short distance between the particles was weakened. The reason that the interaction between the particles of the swellable layered silicate dispersed in this way is weakened is that the particles of the dispersed swellable layered silicate slightly overlap each other between the ends, About tens of swellable phyllosilicates constitute two-dimensional tabular domains, and the distance between the tabular domains must be so large that they cannot interfere with X-ray diffraction. is expected.

In addition, the rheology of the aqueous dispersion of the present invention shows the behavior of a Bingham fluid, and the viscosity increases in the shear test as the number of shear tests increases. This is a very interesting result, and there has been no report of such an extreme increase in shear stress. This fact indicates that in the aqueous dispersion of the present invention, the dispersed particles of the swellable phyllosilicate can overcome the potential barrier between the particles due to shear stress to form a new structure. That is, every time a shear stress is applied,
Bonding between the particles of the swellable layered silicate is promoted, and large two-dimensional domains are grown.

When the solvent is glycols or a mixture of glycols and water in substantially the same amount (weight basis), an X-ray diffraction pattern of a dispersion obtained by mixing a swellable layered silicate with the mixture is used. However, in the X-ray diffraction pattern of the dispersion of the present invention in which a potassium salt is further mixed, the peak becomes smaller and broader as the amount of the potassium salt mixed increases. This is considered to mean that the dispersion state of the swellable phyllosilicate improves as the amount of the potassium salt mixed increases.

The polymer monomer dispersion of the present invention can be obtained by mixing a polymer monomer with the dispersion obtained by the above method. The mixing ratio of the dispersion and the polymer monomer can be arbitrarily selected depending on the purpose, but generally, the amount of the polymer monomer is 5 to 1000 with respect to the raw material swellable phyllosilicate 1 contained in the dispersion. (Weight ratio). In addition,
When the solvent and the polymer monomer are the same substance, the mixing ratio is calculated by regarding the solvent as the polymer monomer.

As the polymer monomer to be mixed, any one can be selected. Typical examples thereof include the above-mentioned polyamide monomer and polyester monomer. When a simple polymerization test was carried out using the polymer monomer dispersion of the present invention, the reflection peak near the (001) diffraction line region of the swellable layered silicate dispersed in the polymer formed after the polymerization was obtained. It was judged that the swellable phyllosilicate was homogeneously dispersed in the polymerized polymer from the fact that it was extremely weak or almost unrecognizable on broad basis, and it was recognized that it was homogeneous by observation. Is done.

[0029]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. In the following examples, potassium salts of reagent grade were used.
In addition, the numerical values of the raw material mixing ratio are on a weight basis unless otherwise specified. As the swellable phyllosilicate, Somasif (ME-100) manufactured by Corp Chemical Co., Ltd. was used. The details of Somasif are described below.

[0030]

_Embedded image General formula: Na _{2X + 2a} Mg _3.0-X [(Si _4.0-a Mg _a ) O ₁₀ ] (F, OH) ₂ (where 0 ≦ X ≦ 0.5, 0 ≦ a <0 .50, 0.15
≦ X + is a ≦ 0.5, Na coordination number 12 cations in the interlayer; Mg _3.0-X in Mg cation coordination number 6 forming the octahedral sheet; (Si _4.0- Si and Mg in _a Mg _a ) are cations having a coordination number of 4 forming a tetrahedral sheet. Cation exchange capacity (methylene blue adsorption amount): 70 meq / 100 g Average particle size 3 μm (Examples 1 to 4) Aqueous dispersion Somasif (swellable layered silicate) and water were mixed, and pyrophosphoric acid was added thereto. Potassium was mixed to obtain four types of dispersions of the present invention having different mixing ratios. The mixing ratio is shown in Table 1. In addition, all the dispersions were in a good dispersion state.

[0031]

[Table 1]

FIG. 1 (1-a) shows the X-ray diffraction pattern of the dispersion of Example 4. For comparison, the X-ray diffraction pattern of the comparative dispersion liquid (1) of Comparative Example 1 is shown in FIG. 1 (1-b). In the case of the dispersion of Example 4, a very weak broad peak was observed at around 15.4 °, but was not observed in the comparative dispersion (1). In addition, the intensity (area below the X-ray diffraction pattern) near 2θ = 1 to 3 degrees (the area below the X-ray diffraction pattern) was weaker (the area was smaller) in the dispersion of Example 4 than in the dispersion (1) for comparison. Can be FIG. 2 shows the results of repeated (four times) shear test using the dispersion of Example 4. This shows that the shear stress increases as the number of shear tests increases.

(Examples 5 to 9) Ethylene glycol dispersion liquid Potassium pyrophosphate was mixed with ethylene glycol and dissolved, and Somasif (swellable layered silicate) was added thereto and mixed, and the mixing ratio was different. Five types of dispersions (or polymer monomer dispersions) of the present invention were obtained. The mixing ratio is shown in Table 2. In addition, all the dispersions were in a good dispersion state.

[0034]

[Table 2]

FIG. 3 is an X-ray diffraction pattern of the dispersions of Examples 5 to 9. For comparison, an X-ray diffraction pattern of the comparative dispersion liquid (2) of Comparative Example 2 is shown in FIG. In both the examples and the comparative examples, there is a reflection peak near 16.9 to 17.0. However, the peak intensity of each of the dispersions of the examples is much smaller than that of the comparative dispersion (2). It can be seen that the peak intensity decreases as the amount of potassium pyrophosphate mixed increases. This is considered to mean that the dispersion state of the swellable phyllosilicate improves as the amount of the potassium salt mixed increases.

(Examples 10 to 15) Dispersions of various potassium salts Somasif (swellable layered silicate) was mixed with water, and various potassium salts were mixed therein. Six dispersions of the invention were obtained. Part 6
Table 3 shows the mixing ratio of each type. In addition, all the dispersions were in a good dispersion state.

[0037]

[Table 3]

FIG. 5 shows the X-ray diffraction patterns of the dispersions of Examples 10 to 15. In each case, a small broad peak is observed around 16.9 to 17.0 °.

(Example 16) 19.7 parts of dimethyl terephthalate was added to 9.7 parts of the dispersion of the present invention obtained in Example 5.
And 3.1 parts of ethylene glycol were mixed to obtain a polymer monomer dispersion of the present invention. 0.04 parts of calcium acetate and 0.08 parts of antimony oxide were added to the polymer monomer dispersion.
Part of the mixture added into a polymerization tube with a side tube of a cooling tube,
While introducing N ₂ gas, put the polymerization tube in an oil bath for 180 minutes.
Heated to ° C. By stirring, a good dispersion was obtained. Thereafter, the temperature of the solution was increased while reducing the pressure inside, and the temperature was maintained at 275 ° C. for 3 hours, then taken out and cooled to synthesize polyethylene terephthalate. The obtained polyethylene terephthalate was measured by an X-ray diffractometer. Since a reflection peak specific to 9 to 15 ° caused by the swellable layered silicate is hardly observed, it is determined that the swellable layered silicate is very fine flaky fine particles and is well dispersed. You.

(Comparative Example 1) 4 parts of Somasif (swellable layered silicate) and 96 parts of water were mixed to obtain Comparative Dispersion (1). (Comparative Example 2) 4 parts of somasif (swellable layered silicate) and 96 parts of ethylene glycol were mixed, and a dispersion for comparison (2)
I got

[0041]

As described above, the swellable layered silicate particles in the dispersion and the polymer monomer dispersion of the present invention constitute two-dimensional domains and are dispersed. It has properties that have not existed in the past, such as presumed characteristics, unique viscosity properties, and good dispersibility. It can be expected to be used as a raw material for imparting, or as a part of a raw material for improving physical properties or imparting properties by mixing with various raw materials, or as a specific viscosity imparting agent.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction pattern of a dispersion.

[Explanation of symbols]

 1-a Dispersion of Example 4 1-b Comparative Dispersion (1)

FIG. 2 is repeated using the dispersion of Example 4 (four times)
It is a figure showing the result of having performed a shearing test.

[Explanation of symbols]

 1 1st 2nd 2nd 3 3rd 3 4th

FIG. 3 is an X-ray diffraction pattern of the dispersions of Examples 5 to 9.

[Explanation of symbols]

 5 Example 5 6 Example 6 7 Example 7 8 Example 8 9 Example 9

FIG. 4 is an X-ray diffraction pattern of a comparative dispersion liquid (2).

FIG. 5 is an X-ray diffraction pattern of the dispersions of Examples 10 to 15.

[Explanation of symbols]

 10 Example 10 11 Example 11 12 Example 12 13 Example 13 14 Example 14 15 Example 15

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 5/05 C08K 5/05 // C08G 63/16 C08G 63/16 (72) Inventor Hiroshi Tateyama 1047-2 Sonezakicho, Tosu-shi, Saga ( 72) Inventor Satoshi Nishimura 2004-4 Maki-cho, Tosu City, Saga Prefecture (72) Inventor Akira Yu Abiko 169-5, Takada-cho, Tosu City, Saga Prefecture (72) Inventor Masaru Oi 1-7802, Makuhari-cho, Hanamigawa-ku, Chiba City, Chiba Prefecture -1 (72) Inventor Noriaki Koseki 2-1-1 Katata, Otsu City, Shiga Prefecture (72) Inventor Yoshiko Takino 2-1-1 Katata, Otsu City, Shiga Prefecture (72) Inventor Nobuyuki Kinan Otsu City, Shiga Prefecture 2-1-1 Katata Examiner Chiyako Inoue (56) References JP-A-3-7729 (JP, A) JP-A-3-41149 (JP, A) JP-A-6-299104 (JP, A) Kaihei 9-309721 (JP, A) WO 97/31973 (WO, A1) WO 91/5736 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09C 1/30 C09C 3/00 C09C 3/0 6

Claims (6)

(57) [Claims] 1. A swellable layered silicate , comprising potassium pyrophosphate
, Potassium triphosphate, potassium polyphosphate, phosphoric acid
Dipotassium monohydrogen, potassium dihydrogen phosphate, potassium sulfate
, Potassium chloride, potassium nitrate and potassium citrate
Water, and a potassium salt selected from the group consisting of
A dispersion obtained by mixing a solvent selected from the group consisting of a mixed solvent with an organic solvent . 2. The method according to claim 1, wherein the swellable phyllosilicate is at the edge of tabular grains.
2. The method according to claim 1, wherein the parts are overlapped and laminated.
A dispersion as described. 3. The method according to claim 1 , which is for producing a polymer.
Is the dispersion described in 2. 4. A polymer monomer dispersion obtained by further mixing a polymer monomer with the dispersion according to any one of claims 1 to 3 . 5. The swellable layered silicate comprises a swellable mica family silicate.
The dispersion according to any one of claims 1 to 4, which is an earth mineral.
liquid. 6. A swellable layered silicate comprising talc and keif
Mix sodium iodide and / or lithium silicofluoride
Obtained by heating the fine powder to 700-1200 ° C.
Alkali gold selected from thorium and / or lithium
Genus, magnesium, silicon, oxygen and fluorine as main constituent elements
5. The swellable layered silicate according to any one of claims 1 to 4.
Or the dispersion according to item 1.